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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Advancing the Performance of Lithium-Rich Oxides in Cooperation with Inherent Complexities: Engineering Domain Structure

The nanodomain structure of lithium- and manganese-rich, composite cathode materials has been systematically altered through synthesis conditions while keeping larger-scale morphological differences to a minimum. Clear changes in electrochemical performance across the samples studied are observed, especially with respect to the anomalous impedance at low states-of-charge. Atomic-scale modeling, coupled to electrochemical measurements and physical characterization, reveals the local consequences of the high-voltage activation charge process as a function of specific domain structures. Furthermore, the results explain the influence of different postactivation structures on the insertion of Li-ions and the associated impedance during discharge. This work adds to our series of studies on lithium- and manganese-rich oxides, demonstrating that the inherent performance of LMRs can be greatly enhanced through rational, highly controlled synthetic strategies based on an understanding of synthesis–structure–property relationships across length scales.

25 ENERGY STORAGE↗
DOE OSTI2021

Engineering Scale Drying of Aluminum-Clad Spent Nuclear Fuel: Experiment Report

Engineering-scale tests were performed to evaluate the relative effectiveness of forced gas and vacuum-drying processes on aluminum-clad spent nuclear fuel (ASNF) in preparation for extended dry storage. Drying models were developed to improve confidence in the likely range of conditions at the start of dry storage and to understand the factors most significant to each process. Testing was performed at the Holtec International Forced Helium Dehydration training facility in Camden, New Jersey, by students from the University of South Carolina in collaboration with Idaho National Laboratory. A full-size Type 1a basket, with a full-diameter vessel configuration (based on the Department of Energy standardized canister design), was used in combination with a 10 assembly surrogate ASNF arrangement to provide a proxy for geometry. A resistance heater incorporated in one assembly simulated the influence of 100 W decay heat. This instrumented chamber allowed testing of the removal of bulk water, physisorbed water, and chemisorbed water over a range of operating parameters with either drying process. Thick oxide films were grown on aluminum test plates to mimic the ASNF surface chemistry. These one-use test plates were housed within select assemblies during drying. Post-test analysis of these plates gave a measure of the moisture removed during each test, which was compared to a control. Instrumentation provided detailed thermal, humidity, and gas or pressure data relevant to each test. Model simulations generally compared favorably to instrument data for the tests. While both processes were able to remove bulk water, removal of chemisorbed water was shown to depend heavily on local temperature. To the disadvantage of vacuum drying, operations approaching or exceeding 220°C achieved consistently more dehydroxylation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

On-Chip Cavity Electroacoustics Using Lithium Niobate Phononic Crystal Resonators

Mechanical systems are pivotal in quantum technologies because of their long coherent time and versatile coupling to qubit systems. So far, the coherent and dynamic control of gigahertz-frequency mechanical modes mostly relies on optomechanical coupling and piezoelectric coupling to superconducting qubits. Here, we demonstrate on-chip cavity electroacoustic dynamics using our microwave-frequency electrically modulated phononic crystal resonators on lithium niobate. Leveraging the high dispersion of phononic crystal, our acoustic modes space unevenly in the frequency spectrum, emulating atomic energy levels. Atomiclike transitions between different acoustic modes are selectively achieved by applying electrical fields to modulate acoustic modes via the nonlinear piezoelectricity of lithium niobate. Among two modes, we demonstrate Autler-Townes splitting, ac Stark shift, and Rabi oscillation with a maximum cooperativity of 4.18. Extending to three modes, we achieve nonreciprocal frequency conversions with an isolation up to 20 dB. Nonreciprocity can be tuned by the time delay between the two modulating pulses. Finally, our cavity electroacoustic platform could find broad applications in sensing, microwave signal processing, acoustic computing, and quantum acoustics.

Rabi model↗
DOE OSTI2024

Discerning molecular-level CO 2 adsorption behavior in amine-modified sorbents within a controlled CO 2 /H 2 O environment towards direct air capture

Sorbents designed for direct air capture (DAC) play a crucial role in the pursuit of achieving net-zero carbon dioxide emissions. This study elucidates CO 2 adsorption from dilute, humidified CO 2 streams onto an amine-modified benchmark DAC adsorbent via solid-state NMR spectroscopy. Various NMR techniques, including 1D 1 H MAS, 13 C MAS, 2D 1 H– 13 C HETCOR NMR, and 1 H R 2 and R 1ρ relaxometry reveal the impact of CO 2 partial pressure and H 2 O on CO 2 adsorption behavior. Here we find that CO 2 concentration governs the stepwise formation of ammonium carbamate, carbamic acid, and physisorbed CO 2 , where relative humidity (RH) at a desired low (<400 ppm) CO 2 loading affects total CO 2 uptake. The relaxation studies reveal the cooperative or competitive nature of H 2 O–CO 2 sorption in CO 2 -dilute humid gas, and in particular polymer swelling upon humidification. From those results, we demonstrate that the observed absorption capacity enhancement by humidity is caused by pore opening due to sorbent swelling, and not by bicarbonate formation. This NMR-discerned speciation provides insights into sorption behavior at different RHs in dilute CO 2 gas streams, simulating real-world atmospheric conditions, and governs the design of efficient and adaptable material-process combinations for solid sorbent DAC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Multiomics and deep learning dissect regulatory syntax in human development

Transcription factors establish cell identity during development by binding regulatory DNA in a sequence-specific manner, often promoting local chromatin accessibility and regulating gene expression1. Mapping accessible chromatin offers critical insights into transcriptional control, but available datasets for human development are restricted to bulk tissue, single organs or single modalities2. Here we present the Human Development Multiomic Atlas, a single-cell atlas of chromatin accessibility and gene expression from 817,740 fetal cells across 12 organs, spanning 203 cell types and more than 1 million candidate cis-regulatory elements, many of which exhibit organ-specific in vivo enhancer activity. Deep learning models trained to predict accessibility from local DNA sequence unravel a comprehensive lexicon of motifs that influence accessibility, including composite motifs exhibiting distinct syntactic constraints that are predicted to mediate transcription factor cooperativity. We identify ‘hard’ syntactic rules requiring precise motif spacing and orientation, ‘soft’ rules allowing flexible motif arrangements, and ubiquitous motifs inhibiting accessibility. Model-based interpretation of genetic variants reveals that disruption of motifs with positive and negative effects is associated with concordant effects on gene expression. Our work delineates how motif syntax governs cell-type-specific chromatin accessibility and provides a foundational resource for decoding cis-regulatory logic and interpreting genetic variation during human development.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Stable Element Doping of Sol-gel Toward Simulating Environmental Matrix in Surrogate Explosive Nuclear Debris

Training nuclear forensic analysis personnel in post-detonation scenarios is of critical importance to nuclear threat response capabilities. Thus, realistic nuclear debris simulants which resemble the size, color, elemental composition, and radionuclide content of actual nuclear fallout from a recent detonation would be valuable for training nuclear first responders in realistic scenarios. As nuclear fallout types vary significantly in each of these parameters based on detonation environment (rural, urban, maritime etc.) and collection location, the ability to tailor each of these parameters accurately in simulated debris would be of immense benefit to the post-detonation analysis community for training both in-field collections and triage and the validation of laboratory level nuclear forensic techniques. Sol-gel synthesis techniques can provide the tunability of size, shape and composition required for producing surrogate nuclear debris of a wide variety. The sol-gel process consists of forming a metal oxide material, often silica, through polymerization of a metal-alkoxy precursor. In this work, we characterize the ability to load the sol-gel particles with secondary elemental components such as iron, aluminum, and calcium toward approximating the elemental composition of debris from various detonation environments and demonstrate the ability to produce particles with controllable size, shape, and color. We also demonstrate quantitative radionuclide encapsulation toward reproducing the radionuclide content of actual fallout from a recent detonation. Finally, we then employ these techniques in producing simulated aerodynamic debris samples with realistic elemental matrix composition and radionuclide content simulating a recent uranium-fueled detonation taking place in a rural desert environment and compare it to historic fallout from the Nevada Nuclear Security Site.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Stable Element Doping of Sol-gel Toward Simulating Environmental Matrix in Surrogate Explosive Nuclear Debris

Training nuclear forensic analysis personnel in post-detonation scenarios is of critical importance to nuclear threat response capabilities. Thus, realistic nuclear debris simulants which resemble the size, color, elemental composition, and radionuclide content of actual nuclear fallout from a recent detonation would be valuable for training nuclear first responders in realistic scenarios. As nuclear fallout types vary significantly in each of these parameters based on detonation environment (rural, urban, maritime etc.) and collection location, the ability to tailor each of these parameters accurately in simulated debris would be of immense benefit to the post-detonation analysis community for training both in-field collections and triage and the validation of laboratory level nuclear forensic techniques. Sol-gel synthesis techniques can provide the tunability of size, shape and composition required for producing surrogate nuclear debris of a wide variety. The sol-gel process consists of forming a metal oxide material, often silica, through polymerization of a metal-alkoxy precursor. In this work, we characterize the ability to load the sol-gel particles with secondary elemental components such as iron, aluminum, and calcium toward approximating the elemental composition of debris from various detonation environments and demonstrate the ability to produce particles with controllable size, shape, and color. We also demonstrate quantitative radionuclide encapsulation toward reproducing the radionuclide content of actual fallout from a recent detonation. Finally, we then employ these techniques in producing simulated aerodynamic debris samples with realistic elemental matrix composition and radionuclide content simulating a recent uranium-fueled detonation taking place in a rural desert environment and compare it to historic fallout from the Nevada Nuclear Security Site.

36 MATERIALS SCIENCE↗
DOE OSTI2020

NREL CITIES Support (CRADA CRD-14-00558 Final Report)

The Technical University of Denmark has received a Grant from the Danish Council for Strategic Research for the project "CITIES - Centre for IT-Intelligent Energy Systems in Cities", a strategic research centre, which involves industrial partners and universities. The Alliance for Sustainable Energy, LLC will participate with DTU as an industrial partner in "CITIES" under this Cooperative Research and Development Agreement (CRADA). The Centre for IT based Intelligent Energy Systems in Cities (CITIES) Project is a Danish national research center focused on work in building short-term operational integrated energy system models that feed longer term plam1ing models, considering the spatio-temporal variations, interactions, dynamics and stochastics in the energy system, from production to consumption. CITIES will harness the extensive expertise and experience of its industrial and academic partners to conduct meaningful research with tangible outputs, including a roadmap to a fossil free future. Decision support tools will be developed to inform stakeholders of the impact of investment, control and policy measures and to identify further opportunities for energy system efficiency. Dissemination and transferring knowledge is a key value to this CRADA, and the use of results by Danish policymakers, industry and society is vital. All participants in the Centre for IT based Intelligent Energy Systems in Cities (CITIES) Project are therefore encouraged to use all means to communicate their findings to society. Wherever possible, and compatible with applicable intellectual property regulations, publications should be produced and disseminated under Open Science, Data, Source and Access principles.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2022

Power Router for Distributing Solar in Communities (Solar Prize): Cooperative Research and Development, CRADA Number CRD-20-16809 (Final Report)

The American Made Solar Prize is a prize competition from the U.S. Department of Energy (DOE) that is designed to revitalize U.S. solar manufacturing. The competition aims to support the growth of U.S. solar manufacturing and reenergize American energy innovation by tapping into American's competitive spirit and the nation's unparalleled innovation ecosystem leveraging national labs, incubators, facilities and more.

14 SOLAR ENERGY↗
DOE OSTI2024

NORTH DAKOTA CARBONSAFE PHASE III: SITE CHARACTERIZATION AND PERMITTING OF GEOLOGIC STORAGE OF CARBON DIOXIDE

The Energy & Environmental Research Center (EERC), in partnership with Minnkota Power Cooperative Inc. (Minnkota), SLB, and Computer Modelling Group Ltd. (CMG), supported wide-scale deployment of carbon capture and storage (CCS) as part of the U.S. Department of Energy (DOE) National Energy Technology Laboratory Carbon Storage Assurance Facility Enterprise (CarbonSAFE) Initiative Phase III. This phase included the acquisition, analysis, and development of information to fully characterize two storage complexes to demonstrate viable storage resources for commercial volumes of CO2 (defined by DOE as a minimum of 50 million tonnes [MMt] of CO2 within a 30-year period) (National Energy Technology Laboratory, 2024). Phase III also involved the preparation, submission, and approval of North Dakota underground injection control (UIC) Class VI storage facility permits (SFPs)—required precursors to applications for Class VI injection well permits. The presumed viability of commercial-scale CCS, situated adjacent to Minnkota’s Milton R. Young Station (MRYS), is validated by Minnkota’s continued pursuit of Project Tundra—an initiative to build the world’s largest lignite-based CCS project in central North Dakota (www.projecttundrand.com). Project Tundra comprises two scopes of work, Tundra Capture (installation of postcombustion CO2 capture at MRYS) and Tundra SGS (secure geologic storage). The efforts of North Dakota CarbonSAFE Phase III, Site Characterization and Permitting, supported Tundra SGS. Extensive site-specific characterization activities included a successful multimeasurement geophysical approach and drilling a stratigraphic test well (J-ROC 1, subsequently renamed Liberty-1) adjacent to MRYS. Core collection and analyses, downhole testing and fluid sampling, and geophysical logging were performed on J-ROC 1 and on a nearby stratigraphic test well (known as J-LOC 1), which was drilled, cored, and tested under a complementary project funded by the North Dakota Lignite Research Program. The injection tests performed on J-LOC 1 positively impacted the CarbonSAFE project, resulting in fewer proposed injection wells and significant construction, operations, and monitoring cost savings. The characterization data collected and analyses performed were integrated into geologic models, and successive numerical simulations were run to determine CO2 plume extent and subsurface pressure buildup associated with the planned CO2 injection rate of nearly 4 MMt per year. The latter doubles the CarbonSAFE Initiative goal with an estimated 100 MMt of CO2 stored in 20 years. Application of the U.S. Environmental Protection Agency’s (EPA’s) method for estimating the Class VI Rule area of review (AOR) to the overpressurized Broom Creek Formation inspired an alternative method of calculation, called risk-based AOR delineation. This peer-reviewed method was applied for the first time during the storage facility-permitting process. The two SFP applications submitted in 2021 successfully resulted in North Dakota Industrial Commission (NDIC) orders in 2022 authorizing the creation of the storage facility areas and amalgamation of pore space as well as establishing financial responsibility requirements. After approval of the SFPs, Minnkota filed in 2022 applications for permits to reenter the J-ROC 1 well and to drill two new wells—all with the intended purpose to become Class VI injection wells. To establish eligibility under the Internal Revenue Code for Section 45Q tax incentives, a monitoring, reporting, and verification (MRV) plan was prepared and submitted by Minnkota to EPA in 2022, resulting in the first such plan approved in North Dakota. Also in 2022, under the National Environmental Policy Act (NEPA), Minnkota prepared and submitted an environmental information volume (EIV) describing the proposed CCS project and associated potential environmental impacts. Based on the EIV, DOE determined that the proposed construction project required an environmental assessment, and Minnkota submitted the first draft in 2023 and a revised draft in 2024. Both submissions were followed by a public comment period. Subsequently, DOE issued a finding of no significant impact (FONSI) on September 13, 2024. A successful outreach program, strongly based in the production, presentation, and dissemination of informational material, fostered an environment to aid stakeholders in making informed decisions regarding the planned project. Opportunities for public input were provided at various steps along the way, including at county planning and zoning meetings, before and during the SFP administrative hearing, and during environmental assessment public comment periods. In addition, land/pore space owners and mineral owners had various points of contact, including granting access rights, securing pore space leasing, and mineral owner notifications. Based upon the successful storage facility permitting issued by NDIC, approval of the MRV plan by EPA, and receipt of a FONSI under the NEPA, Minnkota is continuing its pursuit of Project Tundra. In December 2023, the Office of Clean Energy Demonstrations under its Carbon Capture Demonstrations Projects Program announced funding for the capture system (Office of Clean Energy Demonstrations, 2023) and a proposal for CarbonSAFE Phase IV: Construction funding was submitted in March 2024 for the storage project. A go/no-go decision to proceed with construction and operations in the Broom Creek Formation is anticipated in 2024. References National Energy Technology Laboratory, CarbonSafe Initiative, https://netl.doe.gov/carbon-management/carbon-storage/carbonsafe (accessed August 2024). Office of Clean Energy Demonstrations, 2023, OCED selects three projects in CA, ND, and TX to reduce harmful carbon pollution, create new economic opportunities, and advance carbon reducing technologies, December, www.energy.gov/oced/articles/oced-selects-three-projects-ca-nd-and-tx-reduce-harmful-carbon-pollution-create-new (accessed August 2024).

Peck, Wesley↗
DOE OSTI2020

Drosophila TRIM32 cooperates with glycolytic enzymes to promote cell growth

Cell growth and/or proliferation may require the reprogramming of metabolic pathways, whereby a switch from oxidative to glycolytic metabolism diverts glycolytic intermediates towards anabolic pathways. Herein, we identify a novel role for TRIM32 in the maintenance of glycolytic flux mediated by biochemical interactions with the glycolytic enzymes Aldolase and Phosphoglycerate mutase. Loss of Drosophila TRIM32, encoded by thin (tn), shows reduced levels of glycolytic intermediates and amino acids. This altered metabolic profile correlates with a reduction in the size of glycolytic larval muscle and brain tissue. Consistent with a role for metabolic intermediates in glycolysis-driven biomass production, dietary amino acid supplementation in tn mutants improves muscle mass. Remarkably, TRIM32 is also required for ectopic growth - loss of TRIM32 in a wing disc-associated tumor model reduces glycolytic metabolism and restricts growth. Overall, our results reveal a novel role for TRIM32 for controlling glycolysis in the context of both normal development and tumor growth.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Differential roles of kinetic on- and off-rates in T-cell receptor signal integration revealed with a modified Fab’-DNA ligand

Antibody-derived T-cell receptor (TCR) agonists are commonly used to activate T cells. While antibodies can trigger TCRs regardless of clonotype, they bypass native T cell signal integration mechanisms that rely on monovalent, membrane-associated, and relatively weakly binding ligand in the context of cellular adhesion. Commonly used antibodies and their derivatives bind much more strongly than native peptide major histocompatibility complex (pMHC) ligands bind their cognate TCRs. Because ligand dwell time is a critical parameter that tightly correlates with physiological function of the TCR signaling system, there is a general need, both in research and therapeutics, for universal TCR ligands with controlled kinetic binding parameters. To this end, we have introduced point mutations into recombinantly expressed α-TCRβ H57 Fab to modulate the dwell time of monovalent Fab binding to TCR. When tethered to a supported lipid bilayer via DNA complementation, these monovalent Fab’-DNA ligands activate T cells with potencies well-correlated with their TCR binding dwell time. Single-molecule tracking studies in live T cells reveal that individual binding events between Fab'-DNA ligands and TCRs elicit local signaling responses closely resembling native pMHC. The unique combination of high on- and off-rates of the H57 R97L mutant enables direct observations of cooperative interplay between ligand binding and TCR-proximal condensation of the linker for activation of T cells, which is not readily visualized with pMHC. This work provides insights into how T cells integrate kinetic information from TCR ligands and introduces a method to develop affinity panels for polyclonal T cells, such as cells from a human patient.

Science & Technology - Other Topics↗
DOE OSTI2024

Advanced Measurements for Resilient Integration of Inverter-Based Resources: PROGRESS MATRIX Final Report

As nearly every aspect of the electric power grid undergoes rapid change, measurement technologies that support grid operation and planning must evolve as well. The rapid large-scale deployment of inverter-based resources (IBRs) vital to achieving the nation’s clean energy goals has in some cases led to negative impacts on the reliability and security of the bulk power system (BPS). Advanced power system measurements, including synchronized phasor and waveform measurements, are key to making IBR integration secure and reliable. To this end, the Department of Energy (DOE) initiated the PROGRESS MATRIX project to develop advanced measurement capabilities and analytics that will accelerate adoption of IBRs while improving the reliability and resilience of the BPS. This report discusses the outcomes of the project, which was a joint effort between the Pacific Northwest National Laboratory (PNNL), Oak Ridge National Laboratory (ORNL), the National Renewable Energy Laboratory (NREL), and Lawrence Berkeley National Laboratory (LBNL). In the project’s first year, PNNL, NREL, and ORNL partnered with the Bonneville Power Administration (BPA), the Western Area Power Administration (WAPA), and Kauai Island Utility Cooperative (KIUC) to understand their existing measurement capabilities and the gaps limiting deployment of IBR-focused measurement systems and analytics. The other primary activity in the first year was deployment of GridSweep instruments, which provide unprecedented precision in waveform measurement while probing distribution systems. The instruments were deployed at Dominion Energy and the University of California, Riverside. In the project’s second year, the input from partner utilities and collected measurements were used to advance measurement capabilities. Twelve analytical methods spanning disturbance analysis, power plant evaluation, feeder evaluation, and modeling were developed. Two software tools were developed, one to analyze GridSweep measurements and another to automatically evaluate the control performance of power plants connected to the BPS. Testbeds at ORNL and NREL were augmented to better enable studies of IBR integration. The project culminated in demonstrations of these analytical methods, software tools, and testbeds, both in the field and in the laboratory. This report discusses these various accomplishments and documents the significant progress in developing advanced measurement capabilities to support the secure, reliable, and accelerated adoption of IBRs in the BPS.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2025

Descriptor: Infrastructure Perception and Control: Multi-Sensor Object Tracking Dataset (IPC-MSOT)

Traffic intersections are crucial and challenging nodes in transportation networks where multiple lanes of vehicles and pedestrians converge. Traffic accidents often occur at traffic intersections, including a large proportion of traffic fatalities and about one-half of all traffic injuries in the United States. Object detection data were collected in 2024 across three intersections in Colorado Springs, CO, USA, over the course of multiple days and various times to induce a heterogeneous mix of traffic conditions and behaviors. The purpose of the data collection exercises was to learn various attributes about infrastructure sensors and to build a repository of high-resolution, object-level data that can be used for research and development (e.g., to develop multisensor data fusion algorithms). The Infrastructure Perception and Control:Multi-Sensor Object tracking (IPC-MSOT) dataset was collected as part of the U.S. Department of Transportation's Strengthening Mobility and Revolutionizing Transportation (SMART) project, where the city of Colorado Springs, Colorado, and the National Renewable Energy Laboratory collaborated to collect object-level trajectory data from road users using multiple types of infrastructure sensors deployed at different intersections. This dataset allows for testing of late-stage sensor fusion algorithms and their ability to ingest multimodal sensor data, and it can be utilized by traffic engineers to design and evaluate trajectory-based signal control strategies.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

Cooperation in a fluid swarm of fuel-free micro-swimmers

Abstract While motile bacteria display rich dynamics in dense colonies, the phoretic nature of artificial micro-swimmers restricts their activity when crowded. Here we introduce a new class of synthetic micro-swimmers that are driven solely by light. By coupling a light absorbing particle to a fluid droplet we produce a colloidal chimera that transforms optical power into propulsive thermo-capillary action. The swimmers’ internal drive allows them to operate for a long duration (days) and remain active when crowded, forming a high density fluid phase. We find that above a critical concentration, swimmers form a long lived crowded state that displays internal dynamics. When passive particles are introduced, the dense swimmer phase can re-arrange to spontaneously corral the passive particles. We derive a geometrical, depletion-like condition for corralling by identifying the role the passive particles play in controlling the effective concentration of the micro-swimmers.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Discovery of multidrug efflux pump inhibitors with a novel chemical scaffold

Multidrug efflux is a major contributor to antibiotic resistance in Gram-negative bacterial pathogens. Inhibition of multidrug efflux pumps is a promising approach for reviving the efficacy of existing antibiotics. Previously, inhibitors targeting both the efflux transporter AcrB and the membrane fusion protein AcrA in the Escherichia coli AcrAB-TolC efflux pump were identified. In this work we use existing physicochemical property guidelines to generate a filtered library of compounds for computational docking. We then experimentally test the top candidate coumpounds using in vitro binding assays and in vivo potentiation assays in bacterial strains with controllable permeability barriers. We thus identify a new class of inhibitors of E. coli AcrAB-TolC. Six molecules with a shared scaffold were found to potentiate the antimicrobial activity of erythromycin and novobiocin in hyperporinated E. coli cells. Importantly, these six molecules were also active in wild-type strains of both Acinetobacter baumannii and Klebsiella pneumoniae, potentiating the activity of erythromycin and novobiocin up to 8-fold.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Kinetically Controlled Linker Binding in Rare Earth-2,5-Dihydroxyterepthalic Acid Metal–Organic Frameworks and Its Predicted Effects on Acid Gas Adsorption

In the pursuit of highly stable and selective metal–organic frameworks (MOFs) for the adsorption of caustic acid gas species, an entire series of rare earth MOFs have been explored. Each of the MOFs in this series (RE-DOBDC; RE = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; DOBDC = 2,5-dihydroxyterepthalic acid) was synthesized in the tetragonal space group I4/m. Crystallized MOF samples, specifically Eu-DOBDC, were seen to have a combination of monodentate and bidentate binding when synthesized under typical reaction conditions, resulting in a contortion of the structure. However, extended crystallization times determined that this binding is kinetically controlled and that the monodentate binding option was crystallographically eliminated by extended reaction times at higher temperatures. Furthermore, this series allows for the direct study of the effect of the metal center on the structure of the of the MOF; herein, the lanthanide metal ionic radii contraction across the periodic table results in a reduction of the MOF pore size and lattice parameters. Scanning electron microscopy–energy-dispersive spectroscopy was used to investigate the stages of crystal growth for these RE-DOBDC MOFs. All MOFs, except Er-DOBDC had a minimum of two stages of growth. These analogues were demonstrated by analysis of neutron diffraction (PND) to exhibit a cooperative rotational distortion of the secondary building unit, resulting in two crystallographically distinct linker sublattices. Computational modeling efforts were used to show distinct differences on acid gas (NO 2 and SO 2 ) binding energies for RE-DOBDC MOFs when comparing the monodentate/bidentate combined linker with the bidentate-only linker crystal structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Metal-Tuned Ligand Reactivity Enables CX 2 (X = O, S) Homocoupling with Spectator Cu Centers

Ligand non-innocence is ubiquitous in catalysis with ligands in synthetic complexes contributing as electron reservoirs or co-sites for substrate activation. The latter chemical non-innocence is manifested in H + storage or relay at sites beyond the metal primary coordination sphere. Reaction of a competent CO 2 -to-oxalate reduction catalyst, namely, [K(THF) 3 ](Cu 3 SL), where L 3– is a tris(β-diketiminate) cyclophane, with CS 2 affords tetrathiooxalate at long reaction times or at high CS 2 concentrations, where otherwise an equilibrium is established between the starting species and a complex–CS 2 adduct in which the CS 2 is bound to the C atom on the ligand backbone. X-ray diffraction analysis of this adduct reveals no apparent metal participation, suggesting an entirely ligand-based reaction controlled by the charge state of the cluster. Here, thermodynamic parameters for the formation of the aforementioned Cligand–CS 2 bond were experimentally determined, and trends with cation Lewis acidity were studied, where more acidic cations shift the equilibrium toward the adduct. Relevance of such an adduct in the reduction of CO 2 to oxalate by this complex is supported by DFT studies, similar effects of countercation Lewis acidity on product formation, and the homocoupled heterocumulene product speciation as determined by isotopic labeling studies. Taken together, this system extends chemical non-innocence beyond H + to effect catalytic transformations involving C–C bond formation and represents the rarest example of metal–ligand cooperativity, that is, spectator metal ion(s) and the ligand as the reaction center.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗